EP0046584B1 - Verfahren zum Reinigen cyclischer Dichlorphosphazene, die Spuren protischer Verunreinigungen enthalten - Google Patents

Verfahren zum Reinigen cyclischer Dichlorphosphazene, die Spuren protischer Verunreinigungen enthalten Download PDF

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Publication number
EP0046584B1
EP0046584B1 EP81106526A EP81106526A EP0046584B1 EP 0046584 B1 EP0046584 B1 EP 0046584B1 EP 81106526 A EP81106526 A EP 81106526A EP 81106526 A EP81106526 A EP 81106526A EP 0046584 B1 EP0046584 B1 EP 0046584B1
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Prior art keywords
reactor
boron trihalide
protic impurities
cyclic
cyclic dichlorophosphazene
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EP81106526A
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English (en)
French (fr)
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EP0046584A1 (de
Inventor
John William Fieldhouse
Daniel Frank Graves
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Bridgestone Firestone Inc
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Firestone Tire and Rubber Co
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
    • C01B21/098—Phosphonitrilic dihalides; Polymers thereof
    • C01B21/0986—Phosphonitrilic dichlorides; Polymers thereof

Definitions

  • This invention relates to a method of purifying cyclic dichlorophosphazenes containing trace amounts of protic impurities. More particularly, the invention relates to a method of purifying cyclic dichlorophosphazenes containing protic impurities by treatment with boron trihalides under specified temperature and pressure conditions (described hereinafter).
  • Chlorophosphazenes of the formula (NPC1 2 ) n are conventionally prepared by the reaction of phosphorus pentachloride and ammonium chloride. Chlorophosphazenes prepared by the above reaction are in fact a mixture of compounds consisting of cyclic dichlorophosphazene oligomers such as the cyclic trimer (NPCI 2 ) 3 and tetramer (NPCl 2 ) 4 , low molecular weight oily linear oligomers and certain other unspecified impurities.
  • cyclic dichlorophosphazene oligomers such as the cyclic trimer (NPCI 2 ) 3 and tetramer (NPCl 2 ) 4 , low molecular weight oily linear oligomers and certain other unspecified impurities.
  • the cyclic trimer is the preferred compound for use as the polymerizable monomer in the preparation of high molecular weight linear polydichlorophosphazene polymers, although mixtures containing the cyclic trimer and minor amounts of tetramer are also suitable.
  • Patent No. 3,379,510 contacting molten chlorophosphazenes with an inert solvent vapor so as to selectively vaporize the cyclic trimer, separating a solvent vapor phase laden with trimer and some tetramer from the molten residue, condensing it to form a solution of trimer and tetramer in the solvent and subsequently recovering trimer together with some tetramer from the solution;
  • the method involves the treatment of the oligomer with boron trihalides under appropriate conditions (described below) prior to the polymerization procedure.
  • a process for removing trace amounts of protic impurities from cyclic dichlorophosphazenes represented by the formula (NPC' 2 ) n l wherein n is from 3 to 9, has been developed.
  • the process involves first heating the cyclic dichlorophosphazene in a reactor to a temperature of from about 115 to 150°C. Then, a gaseous or liquid boron trihalide is added to the reactor in an amount in excess of the amount of protic impurities present in the cyclic dichlorophosphazene while maintaining the temperature of the reactor below 150°C.
  • the reactor is pressurized with an inert gas to an internal pressure which is sufficient to permit intimate contact between the cyclic dichlorophosphazene and the boron trihalide. Then, the contents of the reactor are agitated for a sufficient period of time to permit the reaction of substantially all of the protic impurities in the cyclic dichlorophosphazene with the boron trihalide. The reactor is then purged with inert gas to remove the products formed from the reaction of protic impurities and boron trihalide as well as the excess boron trihalide, thereby producing a cyclic dichlorophosphazene which is substantially free of protic impurities.
  • Cyclic dichlorophosphazenes purified by the process of the invention when subjected to catalytic polymerization procedures show increased polymerization rates, higher percentage conversions and more controllable molecular weight of the resultant linear polydichlorophosphazene polymer.
  • the invention relates to a method of removing trace amounts of protic impurities from cyclic dichlorophosphazene oligomers by treating such oligomers with boron trihalides.
  • protic impurities as employed throughout the specification and claims refers to materials which are capable of acting as proton donors.
  • protic as employed herein is in essence the antonym of the term "aprotic”.
  • Protic impurities which may be present in trace amounts in the cyclic dichlorophosphazene oligomers include water, methanol, ethanol, isopropanol, alkyl amines and other basic materials. Of these materials, water is the most common and deleterious impurity present in the cyclic dichlorophosphazene.
  • trace amounts refers to amounts of impurities on the order of parts per million (hereinafter PPM).
  • PPM parts per million
  • the cyclic dichlorophosphazenes which are purified by the process of the invention may contain from 10 to 1000 PPM of such protic impurities.
  • Cyclic dichlorophosphazenes which are purified by the process of the invention are cyclic oligomers represented by the formula (NPC'2),, in which n is an integer of from 3 to 9.
  • a preferred cyclic oligomer for use in the process is the cyclic trimer (NPCI Z ) 3 .
  • the cyclic dichlorophosphazene oligomer containing protic impurities is heated in a suitable reactor to a temperature of from 11 5°C to 150°C.
  • the lower end of the temperature range represents a temperature above the melting point of the oligomer while the upper end of the temperature range represents a temperature below that required to initiate polymerization.
  • the boron trihalide which is employed to treat the cyclic dichlorophosphazene in order to remove the protic impurities may be represented by the general formula BX 3 wherein X is fluorine, chlorine, bromine or iodine.
  • a preferred boron trihalide for such purpose is BC1 3 .
  • the boron trihalide employed in the process can be either in the form of a gas or a liquid with the gaseous boron trihalide being preferred.
  • the amount of boron trihalide utilized in treating the cyclic dichlorophosphazene oligomer to remove trace amounts of protic impurities can be varied somewhat and basically depends upon the amount of protic impurities present in the oligomer.
  • the amount of protic impurities present in these oligomers varies somewhat from lot to lot. Accordingly, the amount of boron trihalide to be used in the pretreatment is from a practical standpoint based upon the amount of water found in the oligomers. This can readily be determined by Karl Fischer water analysis.
  • an excess of boron trihalide is employed in order to assure that all of the protic impurities are removed.
  • the amount of boron trihalide employed is in excess of the total amount of protic impurities present in the cyclic dichlorophosphazene oligomer.
  • the reactor is pressurized with an inert gas to an internal pressure which is sufficient to permit intimate contact between the cyclic dichlorophosphazene oligomer and the boron trihalide.
  • the inert gas employed may be any gas which is unreactive with the cyclic oligomer.
  • a preferred gas for such use is nitrogen.
  • the internal pressure of the reactor is maintained so as to provide intimate contact between the boron trihalide and the cyclic trimer.
  • the internal pressure may be varied from 50 psi (3,45 bar) to 300 psi (20,68 bar). However, it is usually preferred to utilize an internal pressure of 50 psi (3,45 bar).
  • the materials are agitated for a sufficient period of time to permit the reaction of substantially all of the protic impurities present in the cyclic dichlorophosphazene with the boron trihalide.
  • the reaction time is dependent upon factors such as the degree of agitation, temperature and pressure. In general, the reaction time may range from 1 to 4 hours but often 1 to 2 hours are sufficient.
  • the reactor is purged with an inert gas, preferably the same gas used to pressurize the reactor, to remove the products formed from the reaction of protic impurities with boron trihalide as well as any excess boron trihalide, thereby producing a cyclic dichlorophosphazene oligomer which is substantially free of protic impurities.
  • an inert gas preferably the same gas used to pressurize the reactor
  • the purging procedure can be conducted by simply passing the inert gas, e.g., nitrogen, over the head space above the molten trimer and out one of the ports.
  • An alternative and often preferred purging procedure involves sparging dry nitrogen into the bottom of the reactor so as to physically displace any dissolved HCI or excess BCI 3 from the molten trimer and then passing the gas out of the ports. In either case, the purging procedure is repeated until the exiting gas does not contain any HCI or BCI 3 . This can readily be determined by passing the exiting gas into a chloroform solution of dianisylidene acetone. If the exiting gas contains BC1 3 , the solution turns red whereas if it does not the solution will be either pale yellow or colorless.
  • the process of this invention is conducted prior to polymerization of the cyclic dichlorophosphazene oligomers. Accordingly, the purification process can be performed in a separate reactor if desired and the purified oligomer can then be subsequently catalytically polymerized in conventional polymerization equipment. However, it is preferred both from an efficiency standpoint and to prevent possible contamination by protic impurities during handling to conduct the purification process in the polymerization reactor as a pretreatment just prior to polymerization.
  • the boron trihalide reacts with the protic impurities present in the cyclic dichlorophosphazene oligomer. This reaction is believed to proceed by a hydrolysis mechanism in which the boron trihalide is hydrolyzed by the protic impurities.
  • the hydrolysis of boron trichloride by water and alcohols is well known as described in the Articles "Friedel-Crafts and Related Reactions," Volume I, pages 480-481 by G. 0. Olak published by Interscience Publishers in 1963 and "Organoboron Chemistry" Volume I, page 541 by H. Steinberg, published by Interscience Publishers in 1964.
  • the most surprising and unexpected aspect of the process of the invention is that the boric anhydride by product produced by the reaction of boron trihalide and protic impurities such as water does not adversely affect the polymerization of the cyclic oligomer if the hydrogen chloride by product and excess boron trichloride are removed from the reaction zone.
  • Examples (A-F) illustrate the effects of polymerizing cyclic dichlorophosphazene trimer (NPCI2)3 containing trace amounts of water and other protic impurities in the presence of a boron trichloride-triphenyl phosphate catalyst complex.
  • samples of different commercial lots of cyclic trimer (NPCI 2 ) 3 were first analyzed by the Karl Fischer water analysis method to determine the amounts of water present therein. These samples were then polymerized using various levels of a boron trichloride-triphenyl phosphate complex prepared in accordance with the procedure described in our aforementioned US ⁇ A ⁇ 4,226,840.
  • the general polymerization procedure involves charging the trimer and catalyst complex to a 316 stainless steel reactor equipped with thermometer, pressure gauges, ports and mechanical anchor stirrer. The reactor is then heated externally to 220°C for 18-48 hours. Percentage conversion is obtained by vacuum sublimation of a small portion of the polymerizate. A second small portion of the polymerizate is dissolved in a solvent, reprecipitated with a non-solvent, dried, and dissolved in a solvent for determination of intrinsic viscosity [n] which is directly proportional to the molecular weight of the polydichlorophosphazene polymer.
  • Table I shows the results of the Karl Fischer analysis for amounts of water in the various samples of trimer, the amounts of boron trichloride-triphenyl phosphate catalyst employed and the theoretical amount of catalyst destroyed by water.
  • Table II shows the polymerization conditions including weight percentages of trimer and catalyst, temperatures and times and polymerization results such as percentage conversion and intrinsic viscosity.
  • Example A a relatively large amount of catalyst, i.e., 37 mm is utilized in order to effect polymerization. In such case, one would expect to obtain rapid polymerization and high percentage of conversion as well as a polymerizate exhibiting a low molecular weight and intrinsic viscosity. As shown in Table II, these results are obtained. However, as shown in Table I, the starting trimer contains a very small amount of water, i.e., 2.9 mm. Accordingly, 1.9 mm of the catalyst would be destroyed by hydrolysis. Thus, while the polymerization results are not severely affected, the final values, e.g., polymerization rate, percent conversion, molecular weight viscosity, etc. would not reach expected levels.
  • Example B which utilizes the same trimer shows somewhat similar results.
  • a low catalyst level is used which would be expected to result in a polymerizate having higher molecular weight and viscosity values than that of Example A.
  • the presence of water in the trimer results in the destruction of 1.9 mm of catalyst thereby leading to a situation in which the polymerization properties do not reach the expected levels.
  • the levels of water in the starting trimers are very low leading to the destruction of only small amounts of catalyst and therefore drastic effects on the polymerization properties are not obtained.
  • Example C shows similar results to that of Example C.
  • Examples E and F illustrate the even more deleterious effects when the trimer contains high levels of water and low quantities of catalyst are employed.
  • Example E an attempt was made to polymerize a trimer containing 8.5 mm of water with 6.2 mm of added catalyst.
  • Table I the amount of water in the trimer results in the destruction of 5.7 mm of catalyst leaving only 0.5 mm of effective catalyst.
  • the resulting polymerization results show a very low percentage conversion, conversion rate and low intrinsic viscosity and hence low molecular weight. Based on the original amount of catalyst added, i.e., 6.2 mm, one would have expected a high intrinsic viscosity.
  • Example F shows even more drastic effects.
  • Example F an attempt was made to polymerize a trimer containing 13.2 mm of water with 6.4 mm of catalyst. As shown in Table I, this amount of water theoretically will result in the destruction of 8.8 mm of catalyst, more than was actually added. As shown in Table II, the percentage conversion and conversion rate are extremely low and the intrinsic viscosity or molecular weight is also low. Based on the original amount of catalyst charged in Example F, one would have expected a high intrinsic viscosity or molecular weight.
  • Examples (1-3) illustrate the purification of cyclic dichlorophosphazene trimer by pretreatment with boron trichloride in accordance with the process of the invention and the effect of the pretreatment on the subsequent boron trichloride-triphenyl phosphate catalyzed polymerization of the purified trimer.
  • trimer three samples were first analyzed for amounts of water. The trimer was then purified to remove water and other protic impurities by treatment with boron trichloride using the following general procedure:
  • the purified trimer was polymerized with a boron trichloride-triphenyl phosphate catalyst complex immediately following the purging procedure. This was accomplished by adding the desired level of catalyst to the reactor and then raising the temperature to 220°C. The amounts of catalyst, polymerization temperature and time being selected so as to achieve the percent conversion, conversion rate and polymerizate properties (e.g., intrinsic viscosity) desired.
  • Table III shows the results of the analysis of trimer samples for water and the amounts of boron trichloride utilized in the treatment of the trimer samples.
  • Table III also includes the amounts of boron trichloride-triphenyl catalyst employed in the subsequent polymerization and the theoretical amounts of such catalyst which would have have been destroyed in the absence of the boron trichloride purification pretreatment.
  • Table IV shows the results of polymerizing the purified trimer with the boron trichloride-triphenyl catalyst phosphate complex.
  • Example 1 in the absence of the boron trichloride pretreatment, one which would expect the percent conversion, conversion rate and intrinsic viscosity of Example 1 to approximate those of Example D (i.e., 33%, 1.5% per hour, 0.55) based upon the similar millimolar quantities of water in the starting trimers, the same amount of added catalyst and the similar amount of catalyst which would have been destroyed by the water in the trimer.
  • the boron trichloride pretreatment process was employed in Example 1 and, as shown in Table IV, a percent conversion of 61 %, a conversion rate of 2.8% per hour and an intrinsic viscosity of 0.70 were obtained.
  • Example 2 shows a percent conversion of 59.0%, a % conversion per hour of 3.0% and an intrinsic viscosity of 1.60
  • Example 3 shows a percent conversion of 41.0%, a % conversion per hour of 2.9% and an intrinsic viscosity of 1.50.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Catalysts (AREA)

Claims (12)

1. Verfahren zur Reinigung eines cyclischen Dichlorphosphazens, das Spurenmengen von protischen Verunreinigungen enthält, dadurch gekennzeichnet, daß man in Stufen
(a) das cyclische Dichlorphosphazen in einem Reaktor auf eine Temperatur von 115°C bis 150°C erhitzt,
(b) zu dem Reaktor ein gasförmiges oder flüssiges Bortrihalogenid in einer Menge zusetzt, die im Überschuß zu der Menge der in dem cyclischen Dichlorphosphazen vorhandenen protischen Verunreinigungen ist, während man die Temperatur des Reaktors unterhalb 150°C hält.
(c) den Reaktor mit einem inerten Gas auf einen Innendruck unter Druck setzt, der ausreichend ist, daß ein inniger Kontakt zwischen dem cyclischen Dichlorphosphazen und dem Bortrihalogenid gestattet wird,
(d) den Inhalt des Reaktors über einen genügenden Zeitraum durchbewegt, um die Reaktion von im wesentlichen den gesamten protischen Verunreinigungen in dem cyclischen Dichlorphosphazen mit dem Bortrihalogenid zu gestatten, und
(e) den Reaktor mit dem Inertgas spült, um die durch die Reaktion der protischen Verunreinigungen mit dem Bortrihalogenid gebildeten Produkte und überschüssiges Bortrihalogenid zu entfernen, wodurch man ein cyclisches Dichlorphosphazen erzeugt, das im wesentlichen von protischen Verunreinigungen frei ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das cyclische Dichlorphosphazen durch die Formel (NPC'2)nl worin n 3 bis 9 ist, angegeben wird.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Durchbewegungszeit 1 bis 2 Stunden ist.
4. Verfahren zur Herstellung eines linearen Polydichlorphosphazenpolymeren mit hohem Molekulargewicht durch thermische Polymerisation eines cyclischen Dichlorphosphazens der Formel (NPCI2)n' in der n 3 bis 9 ist, in Gegenwart eines Polymerisationskatalysators, umfassend einen Bortrihalogenid- oder Bortrihalogenid-oxygenierten-Phosphorverbindungs-Komplex, dadurch gekennzeichnet, daß man das cyclische Dichlorphosphazen mit einem gasförmigen oder flüssigen Bortrihalogenid vorbehandelt, um Spurenmengen von protischen Verunreinigungen aus dem cyclischen Dichlorphosphazen vor der Einleitung der Polymerisation zu entfernen.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der Polymerisationskatalysator ein Bortrichlorid-Triphenylphosphat-Komplex ist.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Vorbehandlung folgende Stufen umfaßt:
(a) Erhitzen des cyclischen Dichlorphosphazens in einem Reaktor auf eine Temperatur von 115°C bis 150°C,
(b) Zugabe eines gasförmigen oder flüssigen Bortrihalogenids zu dem Reaktor in einer überschüssigen Menge zu der Menge der in dem cyclischen Dichlorphosphazen vorhandenen protischen Verunreinigungen, während die Temperatur des Reaktors unterhalb 150°C gehalten wird,
(c) Unterdrucksetzen des Reaktors mit einem inerten Gas zu einem Innendruck, der ausreichend ist, daß ein inniger Kontakt zwischen dem cyclischen Dichlorphosphazen und dem Bortrihalogenid gestattet wird,
(d) Durchbewegung des Inhalts des Reaktors über einen genügenden Zeitraum, daß die Umsetzung praktisch der gesamten protischen Verunreinigungen in dem cyclischen Dichlorphosphazen mit dem Bortrihalogenid gestattet wird, und
(e) Spülen des Reaktors mit dem Inertgas, um die bei der Umsetzung der protischen Verunreinigungen mit dem Bortrihalogenid gebildeten Produkte und überschüssiges Bortrihalogenid zu entfernen, wodurch ein cyclisches Dichlorphosphazen erzeugt wird, das im wesentlichen von protischen Verunreinigungen frei ist.
7. Verfahren nach Anspruch 1 oder 6, dadurch gekennzeichnet, daß das cyclische Dichlorphosphazen (NPCI2) ist.
8. Verfahren nach Anspruch 1 oder 6, dadurch gekennzeichnet, daß das Bortrihalogenid gasförmiges Bortrihalogenid ist.
9. Verfahren nach Anspruch 1 oder 6, dadurch gekennzeichnet, daß das Bortrihalogenid BC13 ist.
10. Verfahren nach Anspruch 1 oder 6, dadurch gekennzeichnet, daß das inerte Gas Stickstoff ist.
11. Verfahren nach Anspruch 1 oder 6, dadurch gekennzeichnet, daß der Innendruck 50 psi bis 300 psi (3,45 bis 20,68 bar) ist.
12. Verfahren nach Anspruch 1 oder 6, dadurch gekennzeichnet, daß der Innendruck 50 psi (3,45 bar) ist.
EP81106526A 1980-08-25 1981-08-21 Verfahren zum Reinigen cyclischer Dichlorphosphazene, die Spuren protischer Verunreinigungen enthalten Expired EP0046584B1 (de)

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US181028 1980-08-25
US06/181,028 US4327063A (en) 1980-08-25 1980-08-25 Method of purifying cyclic dichlorophosphazenes containing trace amounts of protic impurities

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EP0046584B1 true EP0046584B1 (de) 1983-12-07

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EP (1) EP0046584B1 (de)
JP (2) JPS5945602B2 (de)
CA (1) CA1145114A (de)
DE (1) DE3161594D1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4221854A1 (de) * 1992-07-03 1994-01-05 Nuenchritz Chemie Gmbh Phosphornitridchloride enthaltende Zusammensetzungen und Verfahren zu deren Herstellung

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3144751A1 (de) * 1981-11-11 1983-05-19 Hoechst Ag, 6230 Frankfurt Verfahren zur reinigung von cyclischen chlorphosphazenen
US4544537A (en) * 1984-12-17 1985-10-01 The Firestone Tire & Rubber Company Method for purifying cyclic dichlorophosphazene trimer of catalytic impurities
US4867957A (en) * 1988-04-11 1989-09-19 The United States Of America As Represented By The Secretary Of The Army Process for making polyphosphazenes
IL95939A0 (en) * 1989-10-20 1991-07-18 Atochem Process for compensating the harmful effects of impurities of n-dichlorophosphoryltrichlorophosphazene and its polycondensation product
FR2681061B1 (fr) * 1991-09-11 1993-11-19 Atochem Procede de preparation de polydichlorophosphazenes a partir d'une composition precurseur a base d'hexachlorocyclotriphosphazene.
FR2697008B1 (fr) * 1992-10-15 1994-12-09 Elf Atochem Procédé pour remédier à l'action de l'eau sur les polydichlorophosphazènes.
JP4837963B2 (ja) * 2005-09-20 2011-12-14 濱中ナット株式会社 ねじの弛み止め構造

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Publication number Priority date Publication date Assignee Title
US3952086A (en) * 1974-10-07 1976-04-20 The Firestone Tire & Rubber Company Purification of crude chlorophosphazene compounds by treatment with Bronsted bases
AU502967B2 (en) * 1975-08-22 1979-08-16 Firestone Tire And Rubber Co., The Polymerizing cyclic phosphazenes
JPS537100A (en) * 1976-07-09 1978-01-23 Hitachi Ltd System for setting magnetic moment of artificial satellite
US4116891A (en) * 1976-12-06 1978-09-26 Armstrong Cork Company Catalytic process for the preparation of phosphazene polymers
US4175113A (en) * 1978-04-20 1979-11-20 The Firestone Tire & Rubber Company Purification of crude chlorophosphazene compounds by treatment with water
US4226840A (en) * 1979-09-19 1980-10-07 The Firestone Tire & Rubber Company Process for the polymerization of cyclic polyhalophosphazenes using a catalyst composition of boron trihalide and oxygenated phosphorus compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4221854A1 (de) * 1992-07-03 1994-01-05 Nuenchritz Chemie Gmbh Phosphornitridchloride enthaltende Zusammensetzungen und Verfahren zu deren Herstellung

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EP0046584A1 (de) 1982-03-03
US4327063A (en) 1982-04-27
JPS6027609A (ja) 1985-02-12
CA1145114A (en) 1983-04-26
DE3161594D1 (en) 1984-01-12
JPS623085B2 (de) 1987-01-23
JPS5771808A (en) 1982-05-04
JPS5945602B2 (ja) 1984-11-07

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